Mixtures of water-insoluble disazo dyestuffs and process for preparing them



United States Patent 3,529,984 MIXTURES F WATER-INSOLUBLE DISAZODYESTUFFS AND PROCESS FOR PREPAR- ING THEM Wolfgang Bandel, Kelkheim,Taunus, and Joachim Ribka, Offenbach am Main, Germany, assignors toFarbwerke Hoechst Aktiengesellschaft vormals Meister Lucius & Bruning,Frankfurt am Main, Germany, a corporation of Germany No Drawing. FiledAug. 11, 1966, Ser. No. 571,703 Claims priority, application Germany,Aug. 14, 1965, F 46 07 Int. or. 06811 17/14 US. Cl. 106-288 11 ClaimsABSTRACT OF THE DISCLOSURE The present invention relates to mixtures ofwaterinsoluble disazo-dyestuffs and to a process for preparing them; inparticular it relates to new, water-insoluble disazo dyestuif mixturesconsisting of one asymmetrical dyestuif each of the general formula CH3CH3 and two symmetrical dyestufis of the general formulae and It has nowbeen found that water-insoluble disazo dyestuifs of similarly goodproperties are obtained by coupling 1 mol of tetrazotized4,4-diamino-3,3-dichlorodihpenyl with 2 mols of a mixture of twodifferent coupling components A and B corresponding to the generalformulae in which R represents a phenyl radical which may be substitutedby alkylor alkoxy groups or chlorine atoms, or a naphthyl radical, and Rrepresents an aromatic or and i heterocyclic ring which may besubstituted by non-hydrosolubilizing groups, wherein thehydrosolubilizing carboxylic acid, and sulfonic acid groups are notused, provided that if one coupling component is l-acetoacetylamino-Z-methoxybenzene, the other is neitherl-acetoacetylamino-2,4-dimethylbenzene nor 1-acet0acetylamino-2,5-dimethoxy-4-chlorobenzene.

The dyestuffs may be prepared according to known methods by coupling thetetrazotized diamine with a mixture of both coupling components, forexample, in an aqueous medium, suitably in the presence of a nonionic,anion-active or cation-active dispersing agent or in the presence of anorganic solvent such as, for example, pyridine, quinoline ordimethyl-formamide. To improve the quality of the grain of the pigmentsobtained, it may be of advantage to heat, for example to boil theaqueous coupling mixture for some time, with a simultaneous addition ofsmall amounts of an organic solvent, for example pyridine,chlorobenzene, a phthalic acid dialkyl ester or a resin soap.

The two coupling components may be admixed with one another in variousratios, depending on the properties of technical applicability of thepigment to be prepared. The coupling components may be mixed with oneanother for example, in the ratios of 1:1, 5:1, 10: 1, or 20:1. Thedisazo dyestuif mixture obtained consists of one asymmetrical dyestuifof the Formula 1 (Ill 01 N=NB and two symmetrical dyestuffs of theformulae and in which A and B have the above-mentioned Formulae A and B.The proportion of the various disazo dyestuffs of Formulae 1, 2 and 3 inthe disazo dyestuif mixture depends on the ratio by weight of the twocoupling components A and B as well as of the coupling conditions and ofthe coupling energy of both coupling components used. The proportion ofthe new asymmetrical disazo dyestuffs of Formula 1, hitherto unknown,may in particular be determined by means of a mass spectrometer.

As coupling component of Formula A may be used for example,l-acetoacetylamino compounds of the following primary amines: aniline,:isomeric compounds in various positions of aminomethylbenzene,aminoethylbenzene, aminomethoxybenzene, aminoethoxybenzene,aminochlorobenzene, amino-diand trimethylbenzene, aminodimethoxybenzene,aminodichlorobenzene, aminomethylmethoxybenzene,aminomethylethoxybenzene, aminomethylchlorobenzene,aminomethoxychlorobenzene, aminoethoxychlorobenzene,aminodimethylmethoxybenzene, aminodimethylchlorobenzene,aminodimethoxymethylbenzene, aminodiethoxybenzene,aminodimethoxychlorobenzene, aminodiethoxychlorobenzene,aminodichloromethoxybenzene or aminonaphthalenes.

As coupling components of Formula B may be used, for example, thecompounds which are mentioned as suitable for the coupling component ofFormula A. Furthermore, l-acetoacetylamino compounds of primary aminesmay be used which, in addition to the substituents mentioned as couplingcomponents of Formula A may contain in the phenyl radical the followingsubstituents: nitro groups, acetylamino-, benzoylamino, carboxylic acidamide, sulfonic acid amide, trifluormethyl and cyano groups.Furthermore, there can be applied as coupling components of Formula Bl-acetacetylamino compounds of primary heterocyclic amines which may besubstituted by non-hydrosolubilizing groups, for example, pyridine,benzimidazol, benzimidazolone, benzotriazol, benzindazol; carbostyrile,benzothiazol, carbazol or diphenylenoxide.

The disazo dyestuffs obtained according to the invention arewater-insoluble pigments which are distinguished by good fastness tolight and to solvents. They are suitable for dyeing plastic masses,synthetic acid and natural resins, lacquers and lakeformers, for dyeingspinning masses as well as for dyeing and printing paper and textilesaccording to the known pigment printing and dyeing processes. Owing totheir excellent properties of technical applicability the new dyestuffsare especially suitable for the manufacture of printing colours whichare especially distinguished by a good rheological quality of theprinting pastes and high tinctorial strength and transparency of thedyeings.

The following examples serve to illustrate the invention but they arenot intended to limit it thereto, the parts being by weight unlessotherwise stated.

EXAMPLE 1 9.9 parts of 1-acetoacetylamino-4-1nethylbenzene and 9.2 partsof 1-acetoacetylaminobenzene are dissolved at room temperature whilestirring, in a mixture of 160 parts by volume of water and 25 parts byvolume of a 5 N sodium hydroxide solution. This solution is added at 5C., within 30 minutes, while stirring to a solution of 170 parts byvolume of water, 9 parts by volume of glacial acetic acid and 0.75 partof a reaction product of about 20 mols of ethylene oxide on 1 mol ofoctadecyl alcohol. There is obtained a fine suspension to which, at15-20 C. within one hour, the solution of tetrazotized4,4'-diamino-3,3'-dichlorodiphenyl (prepared by stirring 12.65 parts of4,4'-diamino-3,3-dichlorodiphenyl with 61 parts by volume of Nhydrochloric acid and 175 parts by volume of water, by tetrazotizingwith 20 parts by volume of a 5 N sodium nitrite solution and byclarifying the tetrazo solution by means of silica gel). In thisprocess, the pH value of the coupling mixture is kept at about 4 to 4.5by simultaneously adding a dilute aqueous sodium acetate solution.

When coupling is completed, the reaction mixture is combined with anaqueous solution of 5 parts of calcium chloride and an aqueous solutionof 7 parts of resin soap. The whole is heated to 85 C., and kept at thistemperature for 10 minutes and the dyestufl that has formed is separatedby filtration with suction, washed and dried.

A pigment dyestutf is obtained, which, incorporated into a printingcolour suitable for graphical purposes yields yellow dyeings ofexcellent tinctorial strength.

When parts of 1-acetoacetylamino-4-methylbenzene and 4.6 parts of1-acetoacetylaminobenzene are used and processing is carried out in theabove-mentioned manner, a pigment dyestufi is obtained which,incorporated into a printing colour suitable for graphical purposesyields a more reddish yellow dyeing of the same excellent tinctorialstrength. When 5 parts of l-acetoacetylamino- 4-methylbenzene and 13.8parts of l-acetoacetylaminobenzene are used and processing is carriedout in the abovedescribed manner, a pigment dyestuif is obtained which,incorporated into a printing colour suitable for graphical purposesyields a more greenish yellow dyeing of excellent tinctorial strength,too.

When using as a dispersing agent the same amount of dibutylnaphthalenesulfonic acid or oleyl amine acetate instead of 0.75 part of a reactionproduct of about 20 mols of ethylene oxide and 1 mol of octadecylalcohol, a pigment dyestuff is obtained which, incorporated into aprinting colour suitable for graphical purposes yields a moretransparent yellow dyeing of excellent tinctorial strength, too.

EXAMPLE 2 24.9 parts of 1-acetoacetylamino-4-chloro-2-methoxybenzene and18.3 parts of l-acetoacetylaminobenzene are dissolved at roomtemperature in 500 parts by volume of water and 45 parts by volume of a5 N sodium hydroxide solution. The clear solution is introduced at 3 C.within about 30 minutes into a mixture of 650 parts by volume of waterand 15 parts by volume of glacial acetic acid. Then an aqueous solutionof 55 parts of crystallized sodium acetate is added, and coupling iseifected at room temperature within one hour with a solution oftetrazotized 4,4'-diamino-3,3'-dichlorodiphenyl (prepared by stirring25.3 parts of 4,4-diamino-3,3'-dichlorodiphenyl with 122 parts by volumeof 5 N hydrochloric acid and 350 parts by volume of water, tetrazotizingwith 40 parts by volume of a 5 N sodium nitrite solution and clarifyingthe tetrazotized solution by means of silica gel).

When coupling is completed, the mixture is heated to 90-95 C. and keptat this temperature for 20 minutes and the dyestufi is filtered oflfwith suction. It is washed and dried at 60 C.

A pigment dyestuif is obtained which, incorporated into a printingcolour suitable for graphical purposes yields yellow dyeings ofexcellent tinctorial strength and transparency.

When processing is carried out in the above-described manner, but, aftercoupling being terminated, an aqueous emulsion of 3 parts ofo-dichlorobenzene is added to the reaction mixture, then heated to 9095C., kept at this temperature for 20 minutes, the dyestuff thus obtainedis filtered oil with suction and dried at 60 C., a pigment dyestufl? isobtained which, compared to that described above, absorbs relativelylittle oil and which, incorporated into a printing colour suitable forgraphical purposes yields dyeings of high tinctorial strength and goodtransparency.

EXAMPLE 3 30 parts of 1-acetoacetylamino-4-methylbenzene and 10.6 partsof 1-acetoacetylamino-2-methoxybenzene are dissolved at room temperaturewhile stirring, in a mixture of 500 parts by volume of water and 46parts by volume of a 5 N sodium hydroxide solution. An aqueous solutionof 4 parts of a resin soap is added. Then, an aqueous solution of 50parts of crystallized sodium acetate is added, and at about 15 C., anaqueous solution of 20 parts of glacial acetic acid is slowly addedwithin 30 minutes. Within one hour at room temperature, coupling iscarried out with a solution of tetrazotized 4,4'-diamino-3,3'-dichlorodiphenyl (preparation as described in Example 2).

When coupling is completed, the mixture is heated to about C. and keptat this temperature for 30' minutes and the dyestuff is filtered oifwith suction. It is washed and dried at 60 C.

A pigment dyestuif is obtained, which incorporated into a printingcolour suitable for graphical purposes yields a more medium yellowdyeing of excellent tinctorial strength and good transparency.

The following table contains a series of further coupling components Aand B and their molar ratios as well as the tints of the printingsobtained with dyestuffs which have been prepared from these componentsby using tetrazotized 4,4'-diamino-3,3'-dichlorodiphenyl as tetrazocomponents, and whichmay be prepared according to the correspondingindications in Examples 1 to 3.

Molar Coupling component A Coupling component B ratio Tintl-aetigoacetylaminobenzene l-aclg:oacetylamino-Z-methylbenzene 1 1Medilgm yellow.

0. Do. l-acetoacetylamino-1-naphthylamine Reddish yellow.

1acetoacetylamino-Z-methoxybenzene..

. l-acetoaeetylamino-2,4-dlmethylbenzenel-acetoacetylaminM-methylbenzene Medium yellow.

D0 l-acetoacetylamino-2-ehlorobenzene Do. Dol-(aqetoacetylamino)-benzene-3-sulfonie Do.

acid amide. Do. o Do: 3-acetoacetylammoearbazoL. Do.7-acetoacetylaminoearbostyril D0. Dl-aceigoacetylamino-2,5dimethoxy4-benzoy1- De.

ammobenzene l-acetoacetylamino-4-methy1benzeuel-acetoacetylamm0-2-methoxy-4-chlorobenzene Do.

D o Redclish yellow. Do l-acetoacetylammo-Z,5d1methoxy 4-eh1oro- Dbenzene. ..do Do.

. l-acetoacetylamino i-nitrobenzene1acetoacetylaminoi-acetylaminobenzene Medium yellow. Reddish yellow.

l-acetoacetylamino-4-methy1benzene Medium yellow.

1-acetoacetylamino-3-methoxybenzene 5-acetoacetylamino-benzimidazolon Dl-acetoaeetylamino-2-methoxybenzene l-(aceitioacetylamino)-benzene-4-carboxylic acid am e.

Dol-(acetoacetylemino)-2-methoxybenzene-5- D carboxylic acid amide.l-aeetoacetylamino-z-ethoxybenzenel-acetoacetylamiuo-Z,4-dimethylbenzene D1-acetoacetylamino-2,5-dimethoxybenzene laocetoacetylam1no-2,fi-dimethoxyi-cyano- Yellow.

enzene.

l-acetoacetylamino-2-methoxy-4-chlor0benzene.l-acetoacetylamino-2ethoxybenzenel-aeetoacetylarnino-2-methoxy-5-chlorobenzenel-acetoacetylaminobenzene1-acetoacetylamino-2-methyl-4-chlorobenzene -dol-acetoacetylammo-2-ethoxy-5 acetylaminol-acetoacety1amino-2,4-dimethy1benzene l-acetoaeetylamino-Z-ehlorobenzene l-acetoacetylamino-naphthalene1-acetoacetylamino-2,o-dimethoxyi-die benzene.

l-acetoacetylamino-2,5-dlmethoxy-4-chlor0- benzene.

benzene.

Do- 1-acetoacetylamino-2-methyl-3'ch1orobenzene2-acetoacetylaminonaphthalene 3-acetoacetylamino-pyrid1ne 5acetoacetylammo-benznnidazo l-acetoacet ylamino-Zmethoxy-4-ehlorobenzeneMedium yellow.

Do. Do.

Do. Reddish yellow.

D 0 Medium yellow.

1 l 1 l 1 :1 Do.

Du 6-acetoacetylamino-benztriazol1-aeetoacetylamino2ethoxy-4-ohlorobenzene1acetoacetylamino-2-methylbenzene D Do 2acetoaoetylamnot-ethoxybenzothiazol D 1-acetoacetylamino-3,4-dimethylbenzenel-acetoacetylaml 'hnefihylbenzene Reddish yellow.

1) l-acetoacetylannno-2,5-d1chlorobenzene Medium yellow.

Do 1-acetoacetylarmno-2-chloro-5-trifiuormethyl- D benzene.

W laim; R 1n the above formulae being always different and with 1. Aprocess for the preparation of mixtures of 3 waterinsolubledisazo-dyestufis consisting of one asymmetrlcal dyestuff of the formula(1) CH3 CH3 c1 01 (l) 00 o HN-O o-h worm-@Qmrr-hn-o OATH I l v R:

and two symmetrical dyestuffs of the formula CH3 CH3 and in which Rrepresents phenyl or phenyl substituted by lower alkyl groups, loweralkoxy groups or chlorine atorns, or a naphthyl group, and R representsphenyl or -phenyl substituted by lower alkyl, lower alkoxy, nitro,

trifluoromethyl, cyano, sulfonamide, chlorine, carboxylic acid amide,acetylamino or benzoylamino groups, or a radical of naphthalene,carbazol, carbostyril, bcnzimidazol, benzimidazolon, pyridine,benzindazol, benztnazol, thiazol or ethoxybenzthiazol with the provisothat R and in which R represents phenyl or phenyl substituted by loweralkyl groups, lower alkoxy groups or chlorine and atoms, or a naphthylgroup, and R represents phenyl or phenyl substituted by lower alkyl,lower alkoxy, nitro, trifluoromethyl, cyano, sulfonamide, chlorine,carboxylic acid amide, acetylamino or benzoylamino groups, or a radicalof naphthalene, carbazol, carbostyril, benzimidazol, benzimidazolon,pyridine, benzindazole, benztriazol, thiazol or ethoxy-benzthiazol withthe proviso that R 3. A mixture of Water-insoluble disazo-dyestuifsconsisting of dyestuffs of the formula obtained by coupling 1 moltetrazotized 4,4'-diamino-3,3'- dichlorodiphenyl with 2 mols of amixture consisting of 1-acetoacetylamino-benzene and1-acetoacetylamino-4- methylbenzene, the molar ratio between the twocoupling components being 1:1 to 1:20.

4. A mixture of water-insoluble disazo-dyestulfs consisting of dyestuffsof the formula CH3 CO and 0 H3 0 CH3 WQHMM OCHs and R in the aboveformulae being always different and with the exception that if R is2-methoxy-pheny1- R is neither 2,4-dimethyl-phenyl nor2,5-dimethoxy-4-chlorophenyl, obtained by coupling 1 mol of tetrazotized4,4-diamino-3,3'-dichlorodiphenyl with 2 mols of a mixture of twodifferent coupling components A and B of the formula OCHa I and CH COCHCO-NH-R (B) in which R and R are defined above, the molar ratio OCH3 lOCHa ('10 OCH3 bdsalqiiwmggm Cl CH3 C1 C1 CH3 obtained by coupling 1 moltetrazotized 4,4'-diamino-3,3'- dichlorodiphenyl with 2 mols of amixture consisting of 1-acetoacetylamino-2-methoxy-4-chlorbenzene andl-acetoacetylamino-Z-methylbenezene, the molor ratio between between thetwo coupling components being 1:1 to 1:20. 7 5 the two couplingcomponents being 1:1 to 1:20.

6. A mixture of water-insoluble disazo-dyestuffs consisting of dyestufisof the formula (g C1 C1 I O amino-Z-methoxy-benzene, the molor ratiobetween the two coupling components being 1:1 to 1:20.

OCHs O obtained by coupling 1 mol tetrazotized 4,4'-diarnino-3,3-dichlorodiphenyl with 2 mols of a mixture consisting of to tQHMQBMQQHMHOMQ 8. A mixture of water-insoluble disazo-dyestuffsconsisting of dyestuffs of the formula1-acetoacetylarnino-4-methylbenzene andl-acetoacetylamino-2-methoxy-4-chloro-benzene, the molor ratio betweenthe two coupling components being 121 to 1:20.

7. A mixture of water-insoluble disazo-dyestuifs consisting of dyestuffsof the formula l 0on o0 obtained by coupling 1 mol tetrazotized4,4'-diarnino-3,3- dichlorodiphenyl with 2 mols of a mixture consistingof 1- 0 acetoacetylamino-2-methoxy-4-chlorobenzene and l-acetoand CHOCHa I CH: OCHs and CH3 OCHB OCH OCH

acetylamino-Z-methoxy-benzene, the molor ratio between the two couplingcomponents being 1:1 to 1:20.

9. A mixture of water-insoluble disazo-dyestuffs consisting of dyestuffsof the formula C1 G1 (I; o QHMMHEQCE 1 1 1 2 obtained by'coupling 1 moltetrazotized 4,4'-diamino-3,3'- obtained by coupling 1 mol tetrazotized4,4'i-diamino-3,3'- dichbfodiphenyl Wlth 2 111015 of a mlXtuTeConsisting of dichlorodiphenyl With 2 mols of a mixture consisting of1'acetoacetylammo'Z'methoxy'4'chloro'benzene and1-acetoacetylamino-2-methoxy-4whlor0benzene andl-aceacetoacetylamino-2,5-dimethyl-benzene, the molar ratio between thetwo coupling components being 1:1 to 1:20 toacetylamlno-benzene, themolar ratio between the two 10. A mixture of water-insolubledisazo-dyestuifs con- 5 p g Components bfiing 111 to sisting ofdyestuffs of the formula 0 O(|3Ha I C CH:

i O l OOH: I

and

11. A mixture of water-insoluble disazo-dyestuifs consisting ofdyestuffs of the formula CH1: CH3 CH a A} 01 C1 and CH2: CH: OH I 0011::

References Cited UNITED STATES PATENTS 3,317,331 5/1967 Lenoir et a1106-288 3,446,640 5/ 1969 Orlova et a1. l06-288 OTHER REFERENCES Lubs.:Chemistry of Synthetic Dyes and Pigments, Reinhold Pub. Corp., N.Y.,1955, p. 636.

JAMES E. POER, Primary Examiner

